Process for producing resinous reaction products of sulphur dioxide and olefins



Patented Apr. 12 1938 UNITED .STATES PROCESS FOR PRODUCING RESINOUS RE-ACTION PRODUCTS 0F SULPHUR DIOXIDE AND OLEFINS Louis B. Fitch, Jr., andFrederick, E. Frey, Bartlesvilie, 0kla., assignors to Phillips PetroleumCompany, Bartlesville, 0kla., a corporation of Delaware No Drawing.Application October 19, 1933,'

Serial No. 694,350.

9 Claims. (Cl. 260-2) The present application is a continuation-inpartof our co-pending application- Serial No. 652,771, filed January 20,1933, which is in turn a division of our co-pending application SerialNo. 599,350, filed March 16, 1932.

The present invention relates to the catalytic preparation of resinousreaction products of sulphur dioxide and oleiins, and to catalysts foreifecting such reactions.

A primary object of the invention is the provision of catalysts adaptedto enhance the reaction between sulphur' dioxide and oleilns, and tocause such reaction to take place rapidly even in complete darkness.

Additional objects will become apparent as the description of theinvention proceeds.

While the reaction between sulphur dioxide and certain olefins to form aresin-like product is known, the reaction as therein described, takesplace readily only in the presence of sunlight or some other source ofactinic light.

Y Heat alone has beenfound to be of but limited eiiectiveness inbringing about interaction between sulphur dioxide and oleflns to form aresinlike product. Many oleiins which react rapidly with sulphur dioxidein the presence of light, do not react readily in the dark, even attemperatures somewhat in excess of 100 C. l

According to the present invention, the reactio can be made to take"place in complete darkness in the presence of small amounts of chemicalagents which exert a catalytic effect. It has been found by the addition01' suitable catalysts, the preparation of resinous reaction products ofsulphur dioxide and oleflns may be eflected at low temperatures incomparatively short reaction times, and in the absence of means forproviding actinic light. The catalysts, however, are also eflect'ive inconjunction with elevated temperatures and/or light. I

The catalysts which are suitable for catalyzing the reaction betweensulphur dioxide and olefins under the conditions outlined are oxygen, organic peroxides, salts of silver and monovalent copper, nitric oxide,and nitrogen dioxide. Silver sulphate and sulphite also catalyze thereaction. Cuprous chloride is a catalyst for the reaction.

For example, 2-butene and sulphur dioxide were sealed in liquid mixturein a glass tube with one-hair of one per cent by weight of benzoylperoxide in solution. The reagents were completely converted into asolid-resin on standing for three days in the dark at 80 F. Under the'same conditions, in the absence of a catalyst,

2-bute'ne and sulphur dioxide failed to react to any appreciable extentin the course of three months.-

Withthe same materials and conditions, small quantities of anotherperoxide, diethyl peroxide,

induced the complete conversion of the reagents to resin in four days,Small quantlties' cf silver nitrate induced the reaction. to completion.in thirty minutes.

The aforementioned catalysts have been found useful in inducing andaccelerating the reaction of other olefins such as, ethylene, propylene,butene- 1, pentenel, hexene-l, and isopropyl ethylene, with sulphurdioxide both in the presence and absence of light and diluents. Thereaction of diolefins such as 1,3-butadiene and cyclopentadlene withsulphur dioxide is likewise accelerated by these catalysts.

The products obtained when using the catalysts are similar to thoseobtained when the reaction is carried out in the presence of lightalone. In some cases, however, they may exhibit difierences in softeningtemperatures and other physical characteristics, these differences beingapparently dueto diflerences in the stage oi. polymerization of theproduct, and not to the inclusion of the catalyst in'the product as animpurity. Regardless of how produced, they usually form as a glassy,viscous material in the presence of an excess of sulphur dioxide whichdissolves the resin, except in the case of ethylene, propylene and somedlenes, which yield a resin insoluble in sulphur dioxide.

The catalytic polymerization of these materials is not primarily areaction at the surface of the catalyst, but is principallydue to thepresence of catalyst dissolved'in the olefin-SO: mixture. Particularlyis this noticeable in the inorganic salts,.many-of which, especiallynitrates,

' exhibit marked catalytic effect upon the poly- Where considerablequantites of saturated hy-- drocarbons are present in the reactingmixture, as for example, when a typical butane-butylene cut from an oilcracking operation is reacted withSbz, inorganic nitrate catalystsproduce scarcely any reaction unless added to thereaction mixture inconjunction with a liquid acting as a medium for increasing theirsolubility in the reactingmixture.

Such liquids need not necessarily be used in trate dissolved in sixparts 01' alcohol, acetone,

liquid sulphur dioxide or similar solvent be added to the above mixture,a considerable quantity of reaction product will have formed in one ortwo days, and the addition of more of this catalytic solution at thistime will induce further reaction provided the butenes in the originalmixture are not yet largely converted into resinous product.

What is claimed and desired to be secured by Letters Patent is:'

l. The method of producing high molecular weight heteropolymer's, whichcomprises reacting olefins with sulphur dioxide in the presence or acatalyst consisting of an oxidizing substance of the group:oxygemorganic peroxides.

2. The method 01' producing high molecular weight heteropolymers, whichcomprises reacting olefins with sulphur dioxide in the presence of anorganic peroxide.

3. The method of accelerating the reaction oi sulphur dioxide witholeflns to form high molecular weight heteropolymers, which comprisesconducting the said reaction in the presence of a lower alkyl peroxide.

4. The method of accelerating the reaction of sulphur dioxide witholefins, which comprises conducting the said reaction in the presence ofbenzoyl peroxide. P

5. The method of accelerating the reaction oi sulphur dioxide witholeflns to form high molecu-. lar weight heteropolymers, which comprisesconducting the said reaction in the presence of tree oxygen. r ,i

6. The method of producing high molecular weight heteropolymers, whichcomprises reacting oleflns with sulphur dioxide in the presence of acatalyst consisting of an oxidizing substance of the group: oxygen,organic peroxides; and a liquid medium which increases the solubility ofthe said catalyst in the reaction mixture 01' olefins and sulphurdioxide.

7. The method of producing high molecular weight heteropolymers whichcomprises reacting oleflns with sulphur dioxide in the presence of anorganic peroxide and a lower aliphatic alcohol.

8. The method of producing high molecular weight heteropolymers whichcomprises reacting olefins with sulphur dioxide in the presence of anorganic peroxide which is soluble in the liquid reaction mixture ofoleilns and sulphur dioxide.

9. The method of producing high molecular weight heteropolymers whichcomprises reacting olefins with sulphur dioxide in the presence of alower aliphatic alcohol and a catalyst consisting oi an oxidizingsubstance of the group: oxygen, organic peroxides.

' LOUIS H. FITCH, Jr. FREDERICK E. FREY.

